Color filter and solid state imaging device having a colored pattern formed from a curable composition

ABSTRACT

A color filter or solid state imaging device comprising a colored pattern formed from a curable composition which includes (A) a pigment, (B) a compound having a defined cyclic urea structure and having an acid group or a basic group, (C) a dispersant, (D) a solvent, (E) a radical polymerizable compound, and (F) a photopolymerization initiator. The pigment may be a pigment having a urea structure or an imide structure. The pigment may also be a pigment having a barbituric skeleton.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.12/170,908, filed Jul. 10, 2008, now U.S. Pat. No. 8,008,364 which inturn claims priority under 35 U.S.C. §119 of Japanese Patent ApplicationNo. 2007-184661, filed on Jul. 13, 2007, each hereby expresslyincorporated by reference in its entirety herein.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a pigment dispersion liquid havingexcellent dispersion stability of pigment, a curable composition whichis obtained by using the same and which is suitable for preparing acolor filter to be used for a liquid crystal display (LCD), a solidstate imaging device (for example, a CCD or CMOS) or the like, a colorfiler having a colored pattern formed from the curable composition, anda solid state imaging device.

2. Description of the Related Art

A color filer is an indispensable constitutional component in a liquidcrystal display or a solid state imaging device.

In comparison with a display using a cathode ray tube (CRT: Braun tube)as a display device, a liquid crystal display (LCD) is compact and hasan equal or higher performance. Therefore, LCDs have come to be themainstream for television screens, personal computer screens and otherdisplay apparatus. Also, in recent years, the trend in development ofliquid crystal displays is moving, from conventional monitorapplications in which the screen has a relatively small area, toward TVapplications in which the screen is large and a high image quality isrequired.

In the field of color filters for liquid crystal displays, the substratesize is enlarged in order to produce a large-sized TV, and curing withlow energy is desired for the purpose of improving the productivity whenusing a large-sized substrate. Also, in the field of liquid crystaldisplays for TVs, a higher image quality is required as compared withthat for a conventional monitor. That is, improvements in contrast andcolor purity are required. For the purpose of improving the contrast,with respect to a curable composition to be used in the preparation of acolor filter, a finer particle size is required for a coloring agent(for example, organic pigments) to be used (see, for example, JP-A No.2006-30541). Accompanying this, the addition amount of a dispersant fordispersing a pigment tends to increase. Also, for the purpose ofimproving the color purity, a higher content of a coloring agent (forexample, organic pigments) in the solid content of the curablecomposition is required. Accordingly, the contents of aphotopolymerization initiator and a photopolymerizable monomer in thesolid content of the curable composition tend to decrease.

On the other hand, curing with low energy is also desired in the fieldof color filters for solid state imaging devices. Also, production ofthinner patterns is advancing, and accompanying this, the concentrationof a pigment in the composition is increasing. Furthermore, in a pigmenttype color filter, along with the use of a small particle size pigment,a proportion of a pigment dispersant in the composition tends toincrease.

Also, in order to deal with a problem such as color unevenness, which iscaused since the pigment has relatively coarse particles, a technologyhas been proposed which uses an organic solvent-soluble dye as thecoloring agent in place of the pigment (see, for example, JP-A No.2-127602). However, there are cases where the dye exhibits apolymerization inhibition effect derived from its structure. In a colorfilter in which a dye is used as a coloring agent, since theconcentration of the dye increases, the problem of the polymerizationinhibition effect derived from the dye becomes remarkable, and it isdifficult to realize a high density colored layer using a dye.

Accompanying thinning of the colored layer, the content ratios of acoloring agent in a curable composition for forming the colored layer,namely a pigment and a pigment dispersant, increase, whereas the contentratios of curing components (a polymerizable component and apolymerization initiator) become relatively low. Accordingly, there is aproblem generated in that the sensitivity cannot be sufficientlysecured. Also, the addition amounts of a polymer having a high acidvalue, a development accelerator and the like to be added to the curablecomposition for the purpose of securing developability relativelydecrease, and therefore, there is apprehension that defectivedevelopment is caused.

As described above, in the case where sufficient curability anddevelopability are not obtained, the colored pattern forming propertiesare lowered, and the performance of the obtained color filter isreduced. This problem is remarkable in a solid state imaging devicewhich is required to have fine pattern forming properties.

For the purpose of securing sensitivity and developability, it isdesired to decrease the ratios of a pigment and a pigment dispersant.However, in order to achieve desired color value and spectralcharacteristics, it is not preferable to decrease the content of thepigment, and it is being attempted to decrease the amount of the pigmentdispersant. However, in general, when the amount of the dispersant isdecreased, sufficient dispersion stability of pigment is not obtained,resulting in a problem in that an increase in viscosity is caused overtime.

In particular, in a pigment having a barbituric skeleton, such as yellowpigments, a decrease in dispersion stability of pigment over time isremarkable, and it is the present state that a pigment dispersion liquidwhich is able to achieve stable dispersion with a small amount of adispersant is required.

As described above, in order to realize a colored pattern having asufficient color forming property even in a thin layer, a coloredcurable composition is earnestly desired which has excellent patternforming properties such as sensitivity and developability even in thecase where a coloring agent is contained in a high concentration.

SUMMARY OF THE INVENTION

According to an aspect of the invention, there is provided a pigmentdispersion liquid comprising (A) a pigment, (B) a compound having acyclic urea structure and having an acid group or a basic group, (C) adispersant, and (D) a solvent.

DETAILED DESCRIPTION OF THE INVENTION

The invention is hereunder described in detail.

[Pigment Dispersion Liquid]

The pigment dispersion liquid of the invention comprises (A) a pigment,(B) a compound having a cyclic urea structure and having an acid groupor a basic group, (C) a dispersant, and (D) a solvent. These componentsare successively described below.

First of all, the (B) compound having a cyclic urea structure and havingan acid group or a basic group (this compound will be hereinafterappropriately referred to as “(B) specified compound”), which is acharacteristic component of the invention, is described.

<(B) Compound Having a Cyclic Urea Structure and Having an Acid Group ora Basic Group>

The compound having a cyclic urea structure and having an acid group ora basic group in the invention is a compound having a partial structureof —N—CO—N— in a cyclic structure as represented by the followingformula (I) and having an acid group or a basic partial structure (basicgroup) as a substituent in a molecule thereof.

In the foregoing formula (I), R¹ and R² each independently represent ahydrogen atom, an alkyl group, an aryl group, an alkenyl group or analkynyl group. When R¹ and R² each represent an alkyl group, an arylgroup, an alkenyl group or an alkynyl group, each of these groups mayhave a substituent.

A represents a divalent linking group that links two nitrogen atomsincluded in this ring structure and may be one fused with an aromaticring.

Each of R¹, R² and A may further have a substituent. Examples of thesubstituent which can be introduced include an alkyl group, an arylgroup, an alkenyl group, alkynyl group, a cyclic alkyl group, a cyclicalkenyl group, a cyclic alkynyl group, a hydroxyl group, a thiol group,an ether group, a thioether group, a sulfo group, a sulfonamide group, acarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, athiocarbonyl group, a urea group, a urethane group, an amide group, aheterocyclic group and substituents containing such a group.

However, any one of R¹, R² and A in the formula (I) has an acid group ora basic group.

The acid group or basic group included in the (B) specified compoundsecures dispersibility through a good interaction with an acid groupand/or an amino group included in the (C) dispersant such as adispersion resin to be used for the purpose of stably dispersing thepigment in the solvent. The (B) specified compound forms a goodinteraction with a pigment having an amide group and/or a urea group dueto the cyclic urea structure existing in the molecule thereof, wherebythe dispersion stability is improved.

Examples of the acid group include a phenol group, a carboxyl group, asulfonic acid group, a phosphoric acid group, a sulfinic acid group anda monosulfate ester group.

Examples of the basic group include an amino group, examples of whichinclude a primary amino group, a secondary amino group, a tertiary aminogroup, a cyclic secondary amino group, a cyclic tertiary amino group andan amino group-containing aromatic ring such as a pyridine ring.Conjugate acid groups and conjugate bases thereof can also be used.

From the viewpoint of interaction properties, a carboxyl group, asulfonic acid group and salts thereof are preferable as the acid group;and from the viewpoint of interaction properties, a tertiary amino groupis preferable as the basic group.

The cyclic urea structure is more preferably a 6-membered urea structurerepresented by the following formula (II).

In the formula (II), R¹ and R² are synonymous with those in theforegoing formula (I).

X, Y and Z each independently represent a carbonyl group, an optionallysubstituted methylene group, an oxygen atom, a sulfur atom, —NH— or—NR³—. Here, R³ represents an alkyl group, an aryl group, an alkenylgroup or an alkynyl group. R³ may further have a substituent. Examplesof the substituent which can be introduced include an alkyl group, anaryl group, an alkenyl group, an alkynyl group, a cyclic alkyl group, acyclic alkenyl group, a cyclic alkynyl group, a hydroxyl group, a thiolgroup, an ether group, a thioether group, a sulfo group, a sulfonamidegroup, a carbonyl group, an alkoxycarbonyl group, an aryloxycarbonylgroup, a thiocarbonyl group, a urea group, a urethane group, an amidegroup, a heterocyclic group and substituents containing such a group.

However, at least one of R¹, R², X, Y and Z has an acid group or anamino group.

As the most preferable structure of the (B) specified compound, acompound represented by the following formula (III) is exemplified.

In the formula (III), R¹ and R² are synonymous with those in theforegoing formula (I); and R⁴ and R⁵ each independently represent ahydrogen atom, an alkyl group, an aryl group, an alkenyl group or analkynyl group. Each of R⁴ and R⁵ may further have a substituent.Examples of the substituent which can be introduced include an alkylgroup, an aryl group, an alkenyl group, an alkynyl group, a cyclic alkylgroup, a cyclic alkenyl group, a cyclic alkynyl group, a hydroxyl group,a thiol group, an ether group, a thioether group, a sulfo group, asulfonamide group, a carbonyl group, an alkoxycarbonyl group, anaryloxycarbonyl group, a thiocarbonyl group, a urea group, a urethanegroup, an amide group, a heterocyclic group and substituents containingsuch a group.

Specific examples of the (B) specified compound which can be used in theinvention will be given below, but it should not be construed that theinvention is limited thereto.

The (B) specified compound which can be used in the invention can beobtained by, for example, a method of allowing a barbituric derivativeobtained by a reaction of a compound having a linear urea structure andmalonic acid or a malonic ester to react with an aldehyde in water or anorganic solvent; a method of allowing a compound having a linear ureastructure to react with an alkylating agent; or a method of allowingbarbituric acid or a derivative thereof to react with an aldehyde inwater or an organic solvent. The (B) compound having a cyclic ureastructure and having an acid group or a basic group according to theinvention can be obtained by using a compound having an acid group or abasic group as a raw material for a compound having a linear ureastructure, an aldehyde and an alkylating agent in each of the foregoingreactions, or by synthesizing a compound having a cyclic urea structureby each of the foregoing reactions and then introducing an acid group ora basic group thereinto. The (B) compound having a cyclic urea structureand having an acid group or a basic group according to the invention canalso be synthesized by a method described in JP-A No. 1-34269 and isavailable as a commercial product, too.

In the invention, as to a preferred form of the (B) specified compound,a compound having a 6-membered urea structure is preferable from theviewpoint of dispersion stability, and a compound having a barbituricskeleton is more preferable.

The (B) compound having a cyclic urea structure and having an acid groupor a basic group may be used singly or in combination of two or morekinds thereof in the pigment dispersion liquid.

The content of the (B) compound having a cyclic urea structure andhaving an acid group or a basic group is preferably from 0.1 to 30 partsby mass, more preferably from 0.5 to 20 parts by mass, and furtherpreferably from 1 to 15 parts by mass based on 100 parts by mass of the(A) pigment as described later.

The content of the (B) compound having a cyclic urea structure andhaving an acid group or a basic group is preferably from 0.01 to 20% bymass, and more preferably from 0.05 to 10% by mass in the solid contentof the pigment dispersion liquid of the invention.

<(A) Pigment>

The pigment to be used in the pigment dispersion liquid of the inventionis not particularly limited, and conventionally known various pigmentscan be used singly or in admixture of two or more kinds thereof.

Above all, in view of interaction properties with the (B) compoundhaving a cyclic urea structure and having an acid group or a basicgroup, (A-2) an organic pigment having an amide bond or a urea bond canbe preferably used, and more specifically, an organic pigment having animide group or a urea group is preferable.

In the invention, as the pigment capable of achieving excellentdispersibility when used in combination with the foregoing (B) specifiedcompound, a pigment having a urea group or an imide group is preferable.From such a viewpoint, specific examples thereof include Pigment Yellow120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 167, PigmentYellow 175, Pigment Yellow 180, Pigment Yellow 182, Pigment Yellow 194,Pigment Orange 60, Pigment Orange 62, Pigment Orange 72, Pigment Red123, Pigment Red 149, Pigment Red 171, Pigment Red 175, Pigment Red 176,Pigment Red 178, Pigment Red 179, Pigment Red 185, Pigment Red 190,Pigment Red 208, Pigment Violet 29, Pigment Violet 32, Pigment Blue 80,Pigment Brown 25, Pigment Black 31 and Pigment Black 32.

From the viewpoint of effects, (A-3) a pigment having a barbituricskeleton such as a barbituric group and a barbituric analog is morepreferable. Specific examples thereof include Pigment Yellow 139,Pigment Yellow 150, Pigment Yellow 185, Pigment Orange 64, PigmentOrange 68, Pigment Orange 69 and Pigment Red 260.

The pigment dispersion liquid of the invention is useful for a curablecomposition for forming a colored pattern of a color filter as describedlater. When applying it to such a use, from the viewpoints ofcontrolling color unevenness of the colored pattern to be formed andobtaining high contrast, a primary particle diameter of the pigment ispreferably from 10 to 100 nm, more preferably from 10 to 70 nm, furtherpreferably from 10 to 50 nm, and most preferably from 10 to 40 nm.

These organic pigments can be used singly, or can be used in combinationfor the purpose of increasing color purity.

The blending amount of the pigment to be used in the pigment dispersionliquid of the invention is properly determined depending upon the usepurpose of the pigment dispersion liquid. In general, it is preferablyin the range of from 5 to 80% by mass, and more preferably in the rangeof from 10 to 60% by mass in the solid content of the pigment dispersionliquid.

In the case where the pigment dispersion liquid of the invention is usedfor the curable composition for forming a colored pattern of a colorfilter as described later, the content of the pigment is preferably inthe range of from 20 to 70% by mass, and more preferably in the range offrom 25 to 65% by mass.

In the case where the pigment is used singly, the blending amount of thepigment as referred to herein is a blending amount of the pigment, andin the case where a combination of plural kinds of the pigment isblended, it is the whole amount thereof.

<(C) Dispersant>

For the purpose of securing the dispersion stability of the pigment byenhancing the compatibility with the solvent, the pigment dispersionliquid of the invention contains (C) a dispersant.

The dispersant (pigment dispersant) which can be used in the inventionmay be a high-molecular dispersant (dispersion resin) or a low-molecularweight compound.

Examples of the dispersant which can be favorably used in the inventioninclude high-molecular dispersants (for example, polyamidoamines andsalts thereof, polycarboxylic acids and salts thereof, high-molecularweight unsaturated acid esters, modified polyurethanes, modifiedpolyesters, modified poly(meth)acrylates, (meth)acrylic copolymers andnaphthalenesulfonic acid-formalin condensates), polyoxyethylene alkylphosphates, polyoxyethylene alkylamines, alkanolamines and pigmentderivatives.

The high-molecular dispersant can be further classified into a linearpolymer, a terminal-modified polymer, a graft polymer and a blockpolymer in view of its structure.

The (C) dispersant such as a high-molecular dispersant acts so as toprevent re-aggregation or sedimentation of the pigment through directadsorption on the surface of the pigment or adsorption on the (B)compound having a cyclic urea structure and having an acid group or abasic group, or adsorption on both of them. For that reason, as thehigh-molecular dispersant to be used in the invention, aterminal-modified polymer, a graft polymer and a block polymer, eachhaving an anchor site onto the surface of the pigment, can beexemplified. A dispersant having an acid group or a basic group, whichis able to form an interaction with the (B) specified compound, can alsobe used.

The pigment derivative is an embodiment of the dispersant, which has aneffect of accelerating the adsorption of the high-molecular dispersantby modification of the pigment surface. Accordingly, it is also usefulto use a pigment derivative having a skeleton which is the same as oranalogous to the pigment to be used in combination with thehigh-molecular dispersant.

As the (C) pigment dispersant in the invention, commercially availableproducts can be favorably used, such as DISPERBYK-101 (polyamidoaminephosphate), 107 (carboxylic acid ester), 110 (acid group-containingcopolymer), 130 (polyamide), 161, 162, 163, 164, 165, 166 and 170(high-molecular copolymers) and BYK-P104 and P105 (high-molecular weightunsaturated polycarboxylic acids), all of which are available from BYKChemie; EFKA 4047, 4050, 4010 and 4165 (polyurethane types), EFKA 4330and 4340 (block copolymers), 4400 and 4402 (modified polyacrylates),5010 (polyester amide), 5765 (high-molecular weight polycarboxylic acidsalt), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative) and6750 (azo pigment derivative), all of which are available from EFKA;AJISPER PB821 and PB822, all of which are available from AjinomotoFine-Techno Co., Inc.; FLOWLEN TG-710 (urethane oligomer) and POLYFLOWNo. 50E and No. 300 (acrylic copolymers), all of which are availablefrom Kyoeisha Chemical Co., Ltd.; DISPARLON KS-860, 873SN, 874 and #2150(aliphatic polycarboxylic acids), #7004 (polyether ester), DA-703-50,DA-705 and DA-725, all of which are available from Kusumoto Chemicals,Ltd.; DEMOL RN and N (naphthalenesulfonic acid-formalinpolycondensates), MS, C and SN-B (aromatic sulfonic acid-formalinpolycondensates), HOMOGENOL L-18 (high-molecular polycarboxylic acid),EMULGEN 920, 930, 935 and 985 (polyoxyethylene nonyl phenyl ethers) andACETAMIN 86 (stearylamine acetate), all of which are available from KaoCorporation; SOLSPERSE 5000 (phthalocyanine derivative), 22000 (azopigment derivative), 13240 (polyester amine), 3000, 17000 and 27000(polymers having a functional portion at the terminal thereof), 24000,28000, 32000 and 38500 (graft polymers), all of which are available fromthe Lubrizol Corporation; and NIKKOL T106 (polyoxyethylene sorbitanmonooleate) and MYS-IEX (polyoxyethylene monostearate), all of which areavailable from Nikko Chemicals Co., Ltd.

The (C) dispersant may be used singly or in combination of two or morekinds thereof. In the invention, it is especially preferable to use acombination of a pigment derivative and a high-molecular dispersant asthe (C) dispersant.

The content of the (C) dispersant in the pigment dispersion liquid ofthe invention is preferably from 1 to 150 parts by mass, more preferablyfrom 3 to 100 parts by mass, and further preferably from 5 to 80 partsby mass based on 100 parts by mass of the (A) pigment.

Specifically, when using a high-molecular dispersant, its use amount ispreferably in the range of from 5 to 100 parts by mass, and morepreferably in the range of from 10 to 80 parts by mass based on 100parts by mass of the pigment. When using a pigment derivative, its useamount is preferably in the range of from 1 to 30 parts by mass, morepreferably in the range of from 3 to 20 parts by mass, and especiallypreferably in the range of from 5 to 15 parts by mass based on 100 partsby mass of the pigment.

In the invention, in the case where the pigment dispersion liquid usinga pigment as a coloring agent and a dispersant is applied to a coloredcurable composition as described later, from the viewpoints of curingsensitivity and color density, the total sum of the contents of the (A)pigment and the (C) dispersant is preferably 30% by mass to 90% by mass,more preferably 40% by mass to 85% by mass, and further preferably 50%by mass to 80% by mass relative to the whole of the solid content of thecurable composition.

<(D) Solvent>

The pigment dispersion composition of the invention contains at leastone (D) solvent. By using the (D) solvent together with the foregoing(A) pigment, (B) specified compound and (C) dispersant, a pigmentdispersion composition having the pigment well dispersed therein can beprepared.

As the (D) solvent in the invention, a liquid selected from organicsolvents described below is exemplified. The (D) solvent is chosen whiletaking into account solubility of each of the components to be containedin the pigment dispersion liquid and coating properties when applied tothe curable composition. So far as these desired physical properties aresatisfied, the (D) solvent is not particularly limited. However, it ispreferably chosen while taking into account safety.

Specific examples of the solvent which is preferable include esters, forexample, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate,isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate,butyl butyrate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate,methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate,methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropoinate, ethyl3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate,methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl2-methoxypropionate, ethyl 2-methoxypropionate, propyl2-methoxypropionate, methyl 2-ethoxypropionate, ethyl2-ethoxypropionate, methyl 2-oxyl-2-methylpropionate, ethyl2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propylpyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanateand ethyl 2-oxobutanate;

ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran,ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,methyl cellosolve acetate (ethylene glycol monomethyl ether acetate),ethyl cellosolve acetate (ethylene glycol monoethyl ether acetate),diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,diethylene glycol monobutyl ether, diethylene glycol monoethyl etheracetate, diethylene glycol monobutyl ether acetate, propylene glycolmethyl ether, propylene glycol monomethyl ether acetate, propyleneglycol ethyl ether acetate and propylene glycol propyl ether acetate;

ketones, for example, methyl ethyl ketone, cyclohexanone, 2-heptanoneand 3-heptanone; and aromatic hydrocarbons, for example, toluene andxylene.

Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether,butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone,diethylene glycol monoethyl ether acetate, diethylene glycol monobutylether acetate, propylene glycol methyl ether and propylene glycolmonomethyl ether acetate (PGMEA) are more preferable.

The content of the solvent in the pigment dispersion liquid of theinvention is preferably from 10 to 98% by mass, more preferably from 30to 95% by mass, and most preferably from 50 to 90% by mass. When thecontent of the solvent falls within the foregoing range, the pigment canbe more uniformly dispersed, and such an embodiment is advantageous inview of dispersion stability after dispersion.

It is preferable that the pigment dispersion liquid of the invention isprepared through a mixing and dispersing step of mixing the (A) pigment,the (B) specified compound, the (C) dispersant and other optionalcomponents with the (D) solvent and mixing and dispersing them using amixing machine or dispersion machine. Though the mixing and dispersingstep is preferably composed of kneading dispersion and subsequent finedispersion, the kneading dispersion can be omitted.

[Curable Composition]

The curable composition of the invention includes, in addition to apigment dispersion liquid containing the foregoing (A) pigment, (B)specified compound, (C) dispersant and (D) solvent, (E) a radicalpolymerizable compound and (F) a photopolymerization initiator.

<(E) Radical Polymerizable Compound>

As a general radical polymerizable compound which can be used in theinvention, compounds which are widely known in the industrial field asan ethylenically unsaturated double bond-containing compound can be usedwithout particular limitations. These compounds have a chemical form,for example, a monomer, a prepolymer, namely a dimer, a trimer or anoligomer, and a mixture or copolymer thereof. Examples of the monomerand its copolymer include unsaturated carboxylic acids (for example,acrylic acid, methacrylic acid, itaconic acid, crotonic acid,isocrotonic acid and maleic acid) and esters or amides thereof. Ofthese, esters of an unsaturated carboxylic acid and an aliphaticpolyhydric alcohol compound and amides of an unsaturated carboxylic acidand an aliphatic polyamine compound are preferably used. Additionreaction products of an unsaturated carboxylic acid ester or amidehaving a nucleophilic substituent (for example, a hydroxyl group, anamino group and a mercapto group) and a monofunctional or polyfunctionalisocyanate or epoxy; dehydration condensation reaction products of suchan unsaturated carboxylic acid ester or amide and a monofunctional orpolyfunctional carboxylic acid; and the like are favorably used.Addition reaction products of an unsaturated carboxylic acid ester oramide having an electrophilic substituent (for example, an isocyanategroup and an epoxy group) and a monofunctional or polyfunctionalalcohol, amine or thiol; and displacement reaction products of anunsaturated carboxylic acid ester or amide having an eliminationsubstituent (for example, a halogen group and a tosyloxy group) and amonofunctional or polyfunctional alcohol, amine or thiol are alsofavorable. Alternatively, compounds prepared in the same manner as aboveexcept that an unsaturated phosphonic acid, styrene, vinyl ether, etc.is used in place of the foregoing unsaturated carboxylic acid can alsobe used.

As to the monomer of an ester of an aliphatic polyhydric alcoholcompound and an unsaturated carboxylic acid, specific examples ofacrylic esters include ethylene glycol diacrylate, triethylene glycoldiacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate,propylene glycol diacrylate, neopentyl glycol diacrylate,trimethylolpropane triacrylate, trimethylolpropanetri(acryloyloxypropyl)ether, trimethylolethane triacrylate, hexanedioldiacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycoldiacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate,pentaerythritol tetraacrylate, dipentaerythritol diacrylate,dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitoltetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate,tri(acryloyloxyethyl)isocyanurate and polyester acrylate oligomers.EO-modified products or PO-modified products of these compounds are alsoexemplified.

Examples of methacrylic esters include tetramethylene glycoldimethacrylate, triethylene glycol dimethacrylate, neopentyl glycoldimethacrylate, trimethylolpropane trimethacrylate, trimethylolethanetrimethacrylate, ethylene glycol dimethacrylate, 1,3-butanedioldimethacrylate, hexanediol dimethacrylate, pentaerythritoldimethacrylate, pentaerythritol trimethacrylate, pentaerythritoltetramethacrylate, dipentanerythritol dimethacrylate, dipentaerythritolhexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate,bis[p-(3-methacryloxy-2-hydroxypropoxy)phenyl]dimethylmethane andbis[p-(methacryloxyethoxy)phenyl]dimethylmethane. EO-modified productsor PO-modified products of these compounds are also exemplified.

Examples of itaconic esters include ethylene glycol diitaconate,propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanedioldiitaconate, tetramethylene glycol diitaconate, pentaerythritoldiitaconate and sorbitol tetraitaconate. Examples of crotonic estersinclude ethylene glycol dicrotonate, tetramethylene glycol dicrotonate,pentaerythritol dicrotonate and sorbitol tetradicrotonate. Examples ofisocrotonic esters include ethylene glycol diisocrotonate,pentaerythritol diisocrotonate and sorbitol tetraisocrotonate. Examplesof maleic esters include ethylene glycol dimaleate, triethylene glycoldimaleate, pentaerythritol dimaleate and sorbitol tetramaleate.

As examples of other esters, for example, aliphatic alcohol based estersdescribed in JP-B No. 51-47334 and JP-A No. 57-196231; esters having anaromatic skeleton described in JP-A Nos. 59-5240, 59-5241 and 2-226149;and esters having an amino group described in JP-A No. 1-165613 arefavorably used. Furthermore, the foregoing ester monomers can also beused as a mixture.

Specific examples of monomers of an amide of an aliphatic polyaminecompound and an unsaturated carboxylic acid include methylenebisacrylamide, methylene bismethacrylamide, 1,6-hexamethylenebisacrylamide, 1,6-hexamethylene bismethacrylamide, diethylene triaminetrisacrylamide, xylylene bisacrylamide and xylylene bismethacrylamide.As examples of other preferred amide based monomers, those having acyclohexylene structure described in JP-B No. 54-21726 can beexemplified.

Urethane based addition polymerizable compounds produced through anaddition reaction of an isocyanate and a hydroxyl group are alsofavorable. Specific examples thereof include vinyl urethane compoundscontaining two or more polymerizable vinyl groups in one moleculethereof, which are obtained by adding a hydroxyl group-containing vinylmonomer represented by the following formula (E) to a polyisocyanatecompound having two or more isocyanate groups in one molecule thereof,as described in JP-B No. 48-41708.CH₂═C(R⁴)COOCH₂CH(R⁵)OH   (E)

In the foregoing formula (E), R⁴ and R⁵ each represent H or CH₃.

Urethane acrylates described in JP-A No. 51-37193 and JP-B Nos. 2-32293and 2-16765; and urethane compounds having an ethylene oxide basedskeleton described in JP-B Nos. 58-49860, 56-17654, 62-39417 and62-39418 are also favorable. Furthermore, by using an additionpolymerizable compound having an amino structure or a sulfide structurein a molecule thereof as described in JP-A Nos. 63-277653, 63-260909 and1-105238, a curable composition which is very excellent in photocuringspeed can be obtained.

As other examples, polyester acrylates described in JP-A No. 48-64183and JP-B Nos. 49-43191 and 52-30490; and polyfunctional acrylates ormethacrylates, such as epoxy (meth)acryrates obtained by a reaction ofan epoxy resin and (meth)acrylic acid can be exemplified. Specifiedunsaturated compounds described in JP-B Nos. 46-43946, 1-40337 and1-40336; and vinyl phosphonic acid based compounds described in JP-A No.2-25493 can also be exemplified. In some cases, structures containing aperfluoroalkyl group described in JP-A-61-22048 are favorably used.Furthermore, compounds presented as photocurable monomers and oligomersin Journal of the Adhesion Society of Japan, Vol. 20, No. 7, pages 300to 308 (1984) can be used.

In the invention, in the case where a radical polymerizable compound isadded, from the viewpoint of curing sensitivity, it is preferable thattwo or more ethylenically unsaturated bonds are contained; and it ismore preferable that three or more ethylenically unsaturated bonds arecontained. Above all, it is preferable that two or more (meth)acrylicester structures are contained; it is more preferable that three or more(meth)acrylic ester structures are contained; and it is the mostpreferable that four or more (meth)acrylic ester structures arecontained. Furthermore, from the viewpoints of curing sensitivity anddevelopability in an unexposed area, it is preferable that anEO-modified product is contained. From the viewpoints of curingsensitivity and strength in an exposed area, it is preferable that aurethane bond is contained.

From the foregoing viewpoints, there are preferably exemplifiedbisphenol A diacrylate, a bisphenol A diacrylate EO-modified product,trimethylolpropane triacrylate, trimethylolpropanetri(acryloyloxypropyl)ether, trimethylolethane triacrylate,tetraethylene glycol diacrylate, pentaerythritol diacrylate,pentaerythritol triacrylate, pentaerythritol tetraacrylate,dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate,dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitoltetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate,tri(acryloyloxyethyl)isocyanurate, a pentaerythritol tetraacrylateEO-modified product and a dipentaerythritol hexaacrylate EO-modifiedproduct. As commercially available products, urethane oligomers such asUAS-10 and UAB-140 (all of which are available from Sanyo-Kokusaku PulpCo., Ltd.); DPHA-40H (available from Nippon Kayaku Co., Ltd.); andUA-306H, UA-306T, UA-306I, AH-600, T-600 and AI-600 (all of which areavailable from Kyoeisha Chemical Co., Ltd.) are preferable.

Of these, a bisphenol A diacrylate EO-modified product, pentaerythritoltriacrylate, pentaerythritol tetraacrylate, dipentaerythritolpentaacrylate, dipentaerythritol hexaacrylate,tri(acryloyloxyethyl)isocyanurate, a pentaerythritol tetraacrylateEO-modified product and a dipentaerythritol hexaacrylate EO-modifiedproduct; and DPHA-40H (available from Nippon Kayaku Co., Ltd.) andUA-306H, UA-306T, UA-306I, AH-600, T-600 and AI-600 (all of which areavailable from Kyoeisha Chemical Co., Ltd.) as commercially availableproducts are more preferable.

The content of the (E) radical polymerizable compound in the curablecomposition of the invention is preferably from 1 to 90% by mass, morepreferably from 5 to 80% by mass, and further preferably from 10 to 70%by mass relative to the whole of the solid content of the curablecomposition.

In particular, in the case where the curable composition of theinvention is used for the formation of a colored pattern of a colorfilter, in view of further improving photosensitivity, adhesion to asupport and degree of curing, the content of the (E) radicalpolymerizable compound is preferably from 5 to 50% by mass, morepreferably from 7 to 40% by mass, and further preferably from 10 to 35%by mass relative to the whole of the solid content of the curablecomposition of the invention.

<(F) Photopolymerization Initiator>

The curable composition of the invention contains a photopolymerizationinitiator.

The photopolymerization initiator in the invention is a compound capableof initiating and accelerating polymerization of the foregoing (E)radical polymerizable compound upon decomposition with light andpreferably has absorption in a wavelength region of from 300 to 500 nm.The photopolymerization initiator can be used singly or in combinationof two or more kinds thereof.

Examples of the photopolymerization initiator include organichalogenated compounds, oxydiazole compounds, carbonyl compounds, ketalcompounds, benzoin compounds, acridine compounds, organic peroxidecompounds, azo compounds, coumarin compounds, azide compounds,metallocene compounds, hexaaryl biimidazole compounds, organic boricacid compounds, disulfonic acid compounds, oxime ester compounds, oniumsalt compounds and acyl phosphine (oxide) compounds.

As the organic halogenated compounds, there are specifically exemplifiedcompounds described in Wakabayashi, et al., Bull Chem. Soc. Japan, Vol.42, 2924 (1969), U.S. Pat. No. 3,905,815, JP-B No. 46-4605, JP-A Nos.48-36281, 55-32070, 60-239736, 61-169835, 61-169837, 62-58241,62-212401, 63-70243 and 63-298339 and M. P. Hutt, Journal ofHeterocyclic Chemistry, Vol. 1 (No. 3), 1970; and especially oxazolecompounds and s-triazine compounds having a trihalomethyl groupsubstituted thereon.

As the s-triazine compounds, there are more favorably exemplifieds-triazine derivatives in which at least one mono-, di- ortrihalogen-substituted methyl group is bound to an s-triazine ring.Specific examples thereof include2,4,6-tris(monochloromethyl)-s-triazine,2,4,6-tris(dichloromethyl)-s-triazine,2,4,6-tris(trichloromethyl)-s-triazine,2-methyl-4,6-bis(trichloromethyl)-s-triazine,2-n-propyl-4,6-bis(trichloromethyl)-s-triazine,2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine,2-phenyl-4,6-bis(trichloromethyl)-s-triazine,2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine,2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine,2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine,2-[1-(p-methoxyphenyl)-2,4-butadienyl]-4,6-bis(trichloromethyl)-s-triazine,2-styryl-4,6-bis(trichloromethyl)-s-triazine,2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine,2-(p-isopropyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine,2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine,2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine,2-phenylthio-4,6-bis(trichloromethyl)-s-triazine,2-benzylthio-4,6-bis(trichloromethyl)-s-triazine,2,4,6-tris(dibromomethyl)-s-triazine,2,4,6-tris(tribromomethyl)-s-triazine,2-methyl-4,6-bis(tribromomethyl)-s-triazine and2-methoxy-4,6-bis(tribromomethyl)-s-triazine.

Examples of the oxydiazole compound include2-trichloromethyl-5-styryl-1,3,4-oxydiazole,2-trichloromethyl-5-(cyanostyryl)-1,3,4-oxydiazole,2-trichloromethyl-5-(naphth-1-yl)-1,3,4-oxydiazole and2-trichloromethyl-5-(4-styryl)styryl-1,3,4-oxydiazole.

Examples of the carbonyl compound include benzophenone derivatives suchas benzophenone, Michler's ketone, 2-methylbenzophenone,3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone,4-bromobenzophenone and 2-carboxybenzophenone; acetophenone derivativessuch as 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone,1-hydroxycyclohexylphenyl ketone, α-hydroxy-2-methylphenylpropanone,1-hydroxy-1-methylethyl-(p-isopropylphenyl)ketone,1-hydroxy-1-(p-dodecylphenyl)ketone,2-methyl-(4′-(methylthio)phenyl)-2-morpholino-1-propanone,1,1,1-trichloromethyl-(p-butylphenyl)ketone and2-benzyl-2-dimethylamino-4-morpholinobutyrophenone; thioxanthonederivatives such as thioxanthone, 2-ethylthioxanthone,2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone,2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone; and benzoicester derivatives such as ethyl p-dimethylaminobenzoate and ethylp-diethylaminobenzoate.

Examples of the ketal compound include benzyl methyl ketal andbenzyl-β-methoxyethyl ethyl acetal.

Examples of the benzoin compound include m-benzoin isopropyl ether,benzoin isobutyl ether, benzoin methyl ether and methyl o-benzoylbenzoate.

Examples of the acridine compound include 9-phenylacridine and1,7-bis(9-acridinyl)heptanes.

Examples of the organic peroxide compound include trimethylcyclohexanoneperoxide, acetylacetone peroxide,1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane,1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)butane,tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzenehydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide,1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide,dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane,2,5-oxanoyl peroxide, succinic acid peroxide, benzoyl peroxide,2,4-dichlorobenzoyl peroxide, diisopropylperoxy dicarbonate,di-2-ethylhexylperoxy dicarbonate, di-2-ethoxyethylperoxy dicarbonate,dimethoxyisopropylperoxy carbonate, di(3-methyl-3-methoxybutyl)peroxydicarbonate, tert-butylperoxy acetate, tert-butylperoxy pivalate,tert-butylperoxy neodecanoate, tert-butylperoxy octanoate,tert-butylperoxy laurate, tersyl carbonate,3,3′,4,4′-tetra(t-butylperoxycarbonyl)benzophenone,3,3′,4,4′-tetra(t-hexylperoxycarbonyl)benzophenone,3,3′,4,4′-tetra(p-isopropylcumylperoxycarbonyl)benzophenone, carbonyldi(t-butylperoxydihydrogendiphthalate), and carbonyldi(t-hexylperoxydihydrogendiphthalate).

Examples of the azo compound include azo compounds described in JP-A No.8-108621.

Examples of the coumarin compound include3-methyl-5-amino((s-triazin-2-yl)amino)-3-phenylcoumarin,3-chloro-5-diethylamino((s-triazin-2-yl)amino)-3-phenylcoumarin and3-butyl-5-dimethylamino ((s-triazin-2-yl)amino)-3-phenylcoumarin.

Examples of the azide compound include organic azide compounds describedin U.S. Pat. Nos. 2,848,328, 2,852,379 and 2,940,853 and2,6-bis(4-azidobenzylidene)-4-ethylcyclohexanone (BAC-E).

Examples of the metallocene compound include various titanocenecompounds described in JP-A Nos. 59-152396, 61-151197, 63-41484, 2-249,2-4705 and 5-83588, for example, dicyclopentadienyl-Ti-bisphenyl,dicyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl,dicyclopentadienyl-Ti-bis-2,4-difluorophen-1-yl,dicyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl,dicyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl,dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl,dimethylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl,dimethylcyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl,dimethylcyclopentadienyl-Ti-bis-2,3,5,6-terafluorophen-1-yl,dimethylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, andiron-allene complexes described in JP-A Nos. 1-304453 and 1-152109.

As the biimidazole compound, for example, hexaaryl biimidazole compounds(lophine dimer compounds) are preferable.

Examples of the hexaaryl biimidazole compound include lophine dimersdescribed in JP-B Nos. 45-37377 and 44-86516; and various compoundsdescribed in JP-B No. 6-29285 and U.S. Pat. Nos. 3,479,185, 4,311,783and 4,622,286, specific examples of which include2,2′-bis(o-chlorophenyl)-4,4′,5,5′-tetraphenyl biimidazole,2,2′-bis(o-bromophenyl)-4,4′,5,5′-tetraphenyl biimidazole,2,2′-bis(o,p-dichlorophenyl)-4,4′,5,5′-tetraphenyl biimidazole,2,2′-bis(o-chlorophenyl)-4,4′,5,5′-tetra(m-methoxyphenyl)biimidazole,2,2′-bis(o,o′-dichlorophenyl)-4,4′,5,5′-tetraphenyl biimidazole,2,2′-bis(o-nitrophenyl)-4,4′,5,5′-tetraphenyl biimidazole,2,2′-bis(o-methylphenyl)-4,4′,5,5′-tetraphenyl biimidazole and2,2′-bis(o-trifluorophenyl)-4,4′,5,5′-tetraphenyl biimidazole.

Specific examples of the organic boric acid salt compound includeorganic boric acid salts described in JP-A No. 62-143044, 62-150242,9-188685, 9-188686, 9-188710, 2000-131837 and 2002-107916, JapanesePatent No. 2764769, Japanese Patent Application No. 2000-310808 and Kunzand Martin, Red Tech '98. Proceeding, April, pages 19 to 22 (1998),Chicago; organoboron sulfonium complexes or organoboron oxosulfoniumcomplexes described in JP-A Nos. 6-157623, 6-175564 and 6-175561;organoboron iodonium complexes described in JP-A Nos. 6-175554 and6-175553; organoboron phosphonium complexes described in JP-A No.9-188710; and organoboron transition metal coordination complexesdescribed in JP-A Nos. 6-348011, 7-128785, 7-140589, 7-306527 and7-292014.

Examples of the disulfone compound include compounds described in JP-ANo. 61-166544 and Japanese Patent Application No. 2001-132318.

Examples of the oxime ester compound include compounds described in J.C. S. Perkin II, 1653 to 1660 (1979), J. C. S. Perkin II, 156 to 162(1979), Journal of Photopolymer Science and Technology, 202 to 232(1995), JP-A Nos. 2000-66385 and 2000-80068 and JP-W No. 2004-534797.

Examples of the onium salt compound include diazonium salts described inS. I. Schlesinger, Photogr. Sci. Eng., 18, 387 (1974) and T. S. Bal, etal., Polymer, 21, 423 (1980); ammonium salts described in U.S. Pat. No.4,069,055 and JP-A No. 4-365049; phosphonium salts described in U.S.Pat. Nos. 4,069,055 and 4,069,056; and iodonium salts described inEuropean Patent No. 104,143, U.S. Pat. Nos. 339,049 and 410,201 and JP-ANos. 2-150848 and 2-296514.

The iodonium salt which can be favorably used in the invention is adiaryl iodonium salt; and from the viewpoint of stability, it ispreferably substituted with two or more electron donating groups such asan alkyl group, an alkoxy group and an aryloxy group. As other preferredform of the sulfonium salt, iodonium salts in which one substituent of atriaryl sulfonium salt has a coumarin or anthraquinone structure andwhich has absorption at 300 nm or more are preferable.

Examples of the sulfonium salt which can be favorably used in theinvention include sulfonium salts described in European Patents Nos.370,693, 390,214, 233,567, 297,443 and 297,442, U.S. Pat. Nos.4,933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444 and 2,833,827and German Patents Nos. 2,904,626, 3,604,580 and 3,604,581. From theviewpoint of stability, those substituted with an electron withdrawinggroup are preferable. It is preferable that a Hammett's value of theelectron withdrawing group is larger than 0. Preferred examples of theelectron withdrawing group include a halogen atom and a carboxyl group.

Examples of other preferred sulfonium salt include iodonium salts inwhich one substituent of a triaryl sulfonium salt has a coumarin oranthraquinone structure and which has absorption at 300 nm or more.Examples of another preferred sulfonium salt include sulfonium salts inwhich a triaryl sulfonium salt has an aryloxy group or an aryl thiogroup as a substituent and which has absorption at 300 nm or more.

Examples of the onium salt compound include selenonium salts describedin J. V. Crivello, et al., Macromolecules, 10(6), 1307 (1977) and J. V.Crivello, et al., J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979);and arsonium salts described in C. S. Wen, et al., Teh. Proc. Conf. Rad.Curing ASIA, page 478, Tokyo, October (1988).

Examples of the acyl phosphine (oxide) compound include IRGACURE 819,DAROCURE 4265 and DAROCURE TPO, all of which are available from CibaSpecialty Chemicals.

From the viewpoint of exposure sensitivity, the (F) photopolymerizationinitiator to be used in the invention is preferably a compound selectedfrom the group consisting of trihalomethyl triazine based compounds,benzyl dimethyl ketal compounds, α-hydroxyketone compounds,α-aminoketone compounds, acyl phosphine based compounds, phosphine oxidebased compounds, metallocene compounds, oxime based compounds, atriallyl imidazole dimer, onium based compounds, benzothiazole basedcompounds, benzophenone based compounds, acetophenone based compoundsand derivatives thereof, cyclopentadiene-benzene-iron complexes andsalts thereof, halomethyl oxadiazole compounds and 3-aryl-substitutedcoumarin compounds.

Of these, at least one compound selected from the group consisting oftrihalomethyl triazine based compounds, α-aminoketone compounds, acylphosphine based compounds, phosphine oxide based compounds, oxime basedcompounds, a triallyl imidazole dimer, onium based compounds,benzophenone based compounds and acetophenone based compounds is morepreferable; and at least one compound selected from the group consistingof trihalomethyl triazine based compounds, α-aminoketone compounds,oxime based compounds, a triallyl imidazole dimer and benzophenone basedcompounds is the most preferable.

In particular, in the case where the curable composition of theinvention is used for the preparation of a solid state imaging devicewith a color filter, since it is necessary to form fine pixels in asharp shape, it is important not only to be cured but also to bedeveloped at a fine unexposed area without residue. From such aviewpoint, triazine based compounds, lophine dimer based compounds andoxime based compounds are especially preferable. In particular, in thesolid state imaging device, when fine pixels are formed, a stepperexposure is employed for the exposure for curing. However, this exposuremachine may be damaged by a halogen, and the addition amount of thephotopolymerization initiator should be controlled at a low level.Therefore, taking into account these points, it may be said that inorder to form a fine colored pattern such as in a solid state imagingdevice, the use of an oxime based compound as the (F)photopolymerization initiator is the most preferable.

The content of the (F) photopolymerization initiator to be contained inthe curable composition of the invention is preferably from 0.1 to 50%by mass, more preferably from 0.5 to 30% by mass, and especiallypreferably from 1 to 20% by mass relative to the whole of the solidcontent of the curable composition. When the content of the (F)photopolymerization initiator falls within the foregoing range,satisfactory sensitivity and pattern forming properties are obtainable.

<Binder Polymer>

In addition to these essential components, for the purposes of improvinga film characteristic, adjusting developability and the like, a binderpolymer can be further used in the curable composition of the invention,if desired. It is preferable to use a linear organic polymer as thebinder. As such a “linear organic polymer”, known materials can bearbitrarily used. In order to make it possible to achieve developmentwith water or development with a weakly alkaline aqueous solution, alinear organic polymer which is soluble or swellable in water or aweakly alkaline aqueous solution is preferably chosen. The linearorganic polymer is chosen and used in view of not only a use as a filmforming agent but a use as water, a weakly alkaline aqueous solution oran organic solvent developer. For example, when a water-soluble organicpolymer is used, development with water becomes possible. Examples ofsuch a linear organic polymer include radical polymers having a carboxylgroup at the side chain thereof, for example, polymers described in JP-ANo. 59-44615, JP-B Nos. 54-34327, 58-12577 and 54-25957 and JP-A Nos.54-92723, 59-53836 and 59-71048, namely resins obtained byhomopolymerizing or copolymerizing a carboxyl group-containing monomer;resins obtained by homopolymerizing or copolymerizing an acidanhydride-containing monomer and hydrolyzing, half-esterifying orhalf-amidating an acid anhydride unit; and epoxy acrylates obtained bymodifying an epoxy resin with an unsaturated monocarboxylic acid and anacid anhydride. Examples of the carboxyl group-containing monomerinclude acrylic acid, methacrylic acid, itaconic acid, crotonic acid,maleic acid, fumaric acid and 4-carboxylstyrene. Examples of the acidanhydride-containing monomer include maleic anhydride.

Similarly, there are exemplified acidic cellulose derivatives having acarboxyl group at a side chain thereof. Besides, polymers obtained byadding a cyclic acid anhydride to a hydroxyl group-containing polymerare useful.

In the case where an alkali-soluble resin is used as the copolymer,monomers other than the above-exemplified monomers can be used as acompound to be copolymerized. Examples of other monomers include thefollowing compounds (1) to (13).

(1) Aliphatic hydroxyl group-containing acrylic esters and methacrylicesters, for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate,3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethylmethacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylateand 4-hydroxybutyl methacrylate.

(2) Alkyl acrylates, for example, methyl acrylate, ethyl acrylate,propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexylacrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate,2-chloroethyl acrylate, glycidyl acrylate, 3,4-epoxycyclohexylmethylacrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate,allyl acrylate, 2-allyloxyethyl acrylate and propargyl acrylate.

(3) Alkyl methacrylates, for example, methyl methacrylate, ethylmethacrylate, propyl methacrylate, butyl methacrylate, isobutylmethacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexylmethacrylate, cyclohexyl methacrylate, benzyl methacrylate,2-chloroethyl methacrylate, glycidyl methacrylate,3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate,2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate,2-allyloxyethyl methacrylate and propargyl methacrylate.

(4) Acrylamides and methacrylamides, for example, acrylamide,methacrylamide, N-methylolacrylamide, N-ethylacrylamide,N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide,N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl-N-phenylacrylamide,vinylacrylamide, vinylmethacrylamide, N,N-diallylacrylamide,N,N-diallylmethacrylamide, allylacrylamide and allylmethacrylamide.

(5) Vinyl ethers, for example, ethyl vinyl ether, 2-chloroethyl vinylether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether,octyl vinyl ether and phenyl vinyl ether.

(6) Vinyl esters, for example, vinyl acetate, vinyl chloroacetate, vinylbutyrate and vinyl benzoate.

(7) Styrenes, for example, styrene, α-methylstyrene, methylstyrene,chloromethylstyrene and p-acetoxystyrene.

(8) Vinyl ketones, for example, methyl vinyl ketone, ethyl vinyl ketone,propyl vinyl ketone and phenyl vinyl ketone.

(9) Olefins, for example, ethylene, propylene, isobutylene, butadieneand isoprene.

(10) N-Vinylpyrrolidone, acrylonitrile, methacrylonitrile, etc.

(11) Unsaturated imides, for example, maleimide, N-acryloylacrylamide,N-acetylmethacrylamide, N-propionylmethacrylamide andN-(p-chlorobenzoyl)methacrylamide.

(12) Methacrylic acid based monomers having a hetero atom bound at theα-position, for example, compounds described in Japanese PatentApplications Nos. 2001-115595 and 2001-115598.

Of these, (meth)acrylic resins having an allyl group or a vinyl estergroup and a carboxyl group at a side chain thereof; alkali-solubleresins having a double bond at a side chain thereof as described in JP-ANos. 2000-187322 and 2002-62698; and alkali-soluble resins having anamide group at a side chain thereof as described in JP-A No. 2001-242612are favorable because they are excellent in balance between filmstrength, sensitivity and developability.

Acid group-containing urethane based binder polymers described in JP-BNos. 7-120040, 7-120041, 7-120042 and 8-12424, JP-A Nos. 63-287944,63-287947 and 1-271741 and Japanese Patent Application No. 10-116232;and urethane based binder polymers having an acid group and a doublebond at a side chain thereof as described in JP-A No. 2002-107918 areadvantageous in view of printing resistance and low-exposure suitabilitybecause they are very excellent in strength.

Acid group-containing acetal-modified polyvinyl alcohol based binderpolymers described in European Patents Nos. 993,966 and 1,204,000 andJP-A No. 2001-318463 are favorable because they are excellent in balancebetween film strength and developability.

Furthermore, as other water-soluble linear organic polymers,polyvinylpyrrolidone, polyethylene oxide and the like are useful. Inorder to increase the strength of a cured film, alcohol-soluble nylons,a polyether of 2,2-bis(4-hydroxyphenyl)propane and epichlorohydrin andthe like are also useful.

A weight average molecular weight of the binder polymer which can beused in the invention is preferably 3,000 or more, and more preferablyin the range of from 5,000 to 300,000; and a number average molecularweight is preferably 1,000 or more, and more preferably in the range offrom 2,000 to 250,000. A polydispersity {(weight average molecularweight)/(number average molecular weight)} is preferably 1 or more, andmore preferably in the range of from 1.1 to 10.

These binder polymers may be any of a random polymer, a block polymer, agraft polymer, etc.

The binder polymer which can be used in the invention can be synthesizedby a conventionally known method. Examples of a solvent which can beused in the synthesis include tetrahydrofuran, ethylene dichloride,cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethyleneglycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethylacetate, diethylene glycol dimethyl ether, 1-methoxy-2-propanol,1-methoxy-2-propyl acetate, N,N-dimethylformamide,N,N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyllactate, dimethyl sulfoxide and water. These solvents are used singly orin admixture of two or more kinds thereof.

Examples of a radical polymerization initiator to be used insynthesizing the binder polymer which can be used include knowncompounds such as azo based initiators and peroxide initiators.

The binder polymer may be added at the time of dispersing a pigment, ormay be added at the time of preparing the curable composition by using adispersion liquid thereof. It is favorable that the binder polymer ispreferably added in an amount of from 0% by weight to 50% by weight, andmore preferably from 2% by weight to 30% by weight in the whole of thesolid content at the time of preparing the curable composition.

In the invention, in the case where the binder polymer is used in theimage formation by alkaline development in a color filter for liquidcrystal or solid state imaging device, it is preferable that the binderpolymer has an acid group and/or a hydrophilic group. Preferred examplesof the acid group include a carboxyl group, a sulfonamide group, asulfonic acid group, a phosphonic acid group and a phenol group. Fromthe viewpoints of developability and sensitivity, an acid value ispreferably from 0.1 mmoles/g to 10 mmoles/g, more preferably from 0.2mmoles/g to 5 mmoles/g, and most preferably from 0.3 mmoles/g to 3mmoles/g.

As the hydrophilic group as referred to herein, metal salts of theforegoing acid groups; salts of an organic cation such as ammonium,phosphonium, sulfonium and iodonium; ammonium salts; and those having ahydroxyl group or an alkylene oxide group are preferable.

<Adhesive Group-Containing Compound>

In the case where the curable composition of the invention is used forforming a colored pattern of a color filter, for the purpose ofimproving adhesion to a substrate, an adhesive group-containing compoundcapable of improving adhesion to a substrate is preferably used therein.

The adhesive group as referred to in the invention can be used so far asit has adhesion to a substrate to be used for a color filter. A compoundhaving adsorption properties to a glass substrate or a silicon substrateis especially preferable.

The adhesive group which such a compound has is preferably a groupselected from acid groups such as a sulfonic acid group, a phosphonicacid group and a carboxyl group; ester groups of these acids; metalsalts of these acids; onium salts of these metals; onium groups such asan ammonium group and a pyridinium group; substituents capable ofgenerating a silanol group upon hydrolysis such as an alkoxysilyl group;ampholytic ionic groups such as a phenolic hydroxyl group and an N-oxidegroup; and chelating groups such as an imino diacetic acid.

From the viewpoint of adhesion, an alkoxysilyl group and/or a hydrolyzedgroup thereof is preferable.

<Other Additives>

In the invention, optionally, it is possible to use a compound having agroup capable of improving developability, or a group capable ofimproving sensitivity such as a carbon-carbon double bond containinggroup or a cyclic alkoxy group. Also, a group having such a function canbe employed by introducing it to another component.

As the group capable of improving developability, a heteroatom-containing functional group is preferable, examples of whichinclude an alkoxy group, an alkoxycarbonyl group, a carboxyl group, ahydroxyl group, an amino group, a urethane group, an amide group, athiol group, a sulfo group and a urea group.

Preferred examples of the group capable of improving sensitivity includea methacryl group, an acryl group, a styryl group, a vinyl ether group,an allyl group, a cyclic alkenyl group, a furyl group, an oxetane group,an epoxy group, a tetrahydrofuran group. From the viewpoint ofsensitivity, a methacryl group, an acryl group and a styryl group arepreferable.

<Sensitizer>

For the purposes of improving radical generation efficiency of a radicalinitiator and making the sensitive wavelength long, the curablecomposition of the invention may contain a sensitizer. The sensitizerwhich can be used in the invention is preferably one capable ofachieving sensitization of the foregoing photopolymerization initiatorthrough an electron transfer mechanism or an energy transfer mechanism.

Examples of the sensitizer which can be used in the invention includethose belonging to the compounds as exemplified below and having anabsorption wavelength in a wavelength region of from 300 nm to 450 nm,preferably from 330 nm to 450 nm.

Examples thereof include polynuclear aromatic compounds (for example,phenanthrene, anthracene, pyrene, perylene, triphenylene and9,10-dialkoxyanthracenes), xanthenes (for example, Fluororescein,Eosine, Erythrocin, Rhodamine B and Rose Bengale), thioxanthones (forexample, isopropylthioxanthone, diethylthioxanthone andchlorothioxanothone), cyanines (for example, Thiacarbocyanine andOxacarbocyanine), merocyanines (for example, merocyanine andcarbomerocyanine), phthalocyanines, thiazines (for example, Thionine,Methylene Blue and Toluidine Blue), acridines (for example, AcridineOrange, chloroflavin and acriflavin), anthraquinones (for example,anthraquinone), squaryliums (for example, squarylium), Acridine Orange,coumarins (for example, 7-diethylamino-4-methylcoumarin), keto-coumarin,phenothiazines, phenazines, styrylbenzenes, azo compounds,diphenylmethane, triphenylmethane, distyrylbenzens, carbazoles,porphyrin, spiro compounds, quinacridone, indigo, styryl, pyryliumcompounds, pyrromethene compounds, pyrazolotriazole compounds,benzothiazole compounds, barbituric acid derivatives, thiobarbituricacid derivatives, aromatic ketone compounds (for example, acetophenone,benzophenone, thioxanthone and Michler's ketone) and heterocycliccompounds (for example, N-aryloxazolidinones). Furthermore, there areexemplified compounds described in European Patent No. 568,993, U.S.Pat. Nos. 4,508,811 and 5,227,227 and JP-A Nos. 2001-125255 and11-271969.

More preferred examples of the sensitizer include compounds representedby the following formulae (i) to (iv).

In the formula (i), A¹ represents a sulfur atom or NR⁵⁰; R⁵⁰ representsan alkyl group or an aryl group; L² represents a non-metal atomic groupwhich forms, together with adjacent A¹ and the adjacent carbon atom, abasic nucleus of a dye; R⁵¹ and R⁵² each independently represent ahydrogen atom or a monovalent non-metal atomic group, and R⁵¹ and R⁵²may be linked to each other to form an acid nucleus of a dye; and Wrepresents an oxygen atom or a sulfur atom.

In the formula (ii), Ar¹ and Ar² each independently represent an arylgroup and are linked to each other via -L³-; L³ represents —O— or —S—;and W is synonymous with that in the formula (i).

In the formula (iii), A² represents a sulfur atom or NR⁵⁹; L⁴ representsa non-metal atomic group which forms, together with adjacent A² and theadjacent carbon atom, a basic nucleus of a dye; R⁵³, R⁵⁴, R⁵⁵, R⁵⁶, R⁵⁷and R⁵⁸ each independently represent a monovalent non-metal atomicgroup; and R⁵⁹ represents an alkyl group or an aryl group.

In the formula (iv), A³ and A⁴ each represent —S—, —NR⁶²— or —NR⁶³—; R⁶²and R⁶³ each independently represent a substituted or unsubstitutedalkyl group or a substituted or unsubstituted aryl group; L⁵ and L⁶ eachindependently represent a non-metal atomic group which forms, togetherwith adjacent A³ or A⁴ and the adjacent carbon atom, a basic nucleus ofa dye; and R⁶⁰ and R⁶¹ each independently represent a monovalentnon-metal atomic group or are able to be linked to each other to form analiphatic or aromatic ring.

Preferred specific examples of the compounds represented by the formulae(i) to (iv) are given below.

The sensitizer may be used singly or in combination of two or more kindsthereof.

From the viewpoints of light absorption efficiency in the depth andinitiation and decomposition efficiency, the content of the sensitizerin the curable composition of the invention is preferably from 0.1 to20% by mass, and more preferably from 0.5 to 15% by mass as a solidcontent.

<Cosensitizer>

It is also preferable that the curable composition of the inventioncontains a cosensitizer. In the invention, the cosensitizer has anaction to more improve sensitivity to active radiations of a sensitizingdye or an initiator or to control polymerization inhibition of apolymerizable compound due to oxygen.

Examples of such a cosensitizer include amines, for example, compoundsdescribed in M. R. Sander, et al., Journal of Polymer Society, Vol. 10,page 3173 (1972), JP-B No. 44-20189, JP-A Nos. 51-82102, 52-134692,59-138205, 60-84305, 62-18537 and 64-33104 and Research Disclosure, No.33825. Specific examples thereof include triethanolamine, ethylp-dimethylaminobenzoate, p-formyldimethylaniline andp-methylthiodimethylaniline.

As other examples of the cosensitizer, there are enumerated thiols andsulfides, for example, thiol compounds described in JP-A No. 53-702,JP-B No. 55-500806 and JP-A No. 5-142772 and disulfide compoundsdescribed in JP-A No. 56-75643. Specific examples thereof include2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole,2-mercapto-4(3H)-quinazoline and β-mercaptonaphthalene.

As other examples of the cosensitizer, there are enumerated amino acidcompounds (for example, N-phenylglycine), organometallic compoundsdescribed in JP-B No. 48-42965 (for example, tributyltin acetate),hydrogen donators described in JP-B No. 55-34414 and sulfur compoundsdescribed in JP-A No. 6-308727 (for example, trithiane).

From the viewpoint of improving the curing speed due to a balancebetween polymerization growth speed and chain transfer, the content ofsuch a cosensitizer is preferably in the range of from 0.1 to 30% bymass, more preferably in the range of from 1 to 25% by mass, and furtherpreferably in the range of from 0.5 to 20% by mass relative to the massof the whole of the solid of the curable composition.

<Polymerization Inhibitor>

In the invention, in order to prevent unnecessary heat polymerization ofa polymerizable, ethylenically unsaturated double bond-containingcompound during the manufacture or preservation of the curablecomposition, it is desirable to add a small amount of a heatpolymerization inhibitor.

Examples of the heat polymerization inhibitor which can be used in theinvention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol,pyrogallol, t-butylcatechol, benzoquinone,4,4′-thiobis(3-methyl-6-t-butylphenol),2,2′-methylenebis(4-methyl-6-t-butylphenol) and cerousN-nitrosophenylhydroxyamine.

The addition amount of the heat polymerization inhibitor is preferablyfrom about 0.01% by mass to about 5% by mass relative to the mass of thewhole composition. For the purpose of preventing polymerizationinhibition due to oxygen, a higher fatty acid derivative such as behenicacid and behenic amide or the like may be added and distributed on thesurface of a photosensitive layer during a step of drying after coatingas the need arises. The addition amount of the higher fatty acidderivative is preferably from about 0.5% by mass to about 10% by mass ofthe whole composition.

<Other Additives>

Furthermore, in the invention, known additives such as inorganic fillersfor improving physical properties of a cured film, plasticizers andlipophilicity agents capable of improving inking properties on thesurface of a photosensitive layer may be added.

Examples of the plasticizer include dioctyl phthalate, didodecylphthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate,tricresyl phosphate, dioctyl adipate, dibutyl sebacate and triacetylglycerin. When a binder is used, the plasticizer can be added in anamount of not more than 10% by mass relative to the total mass of theethylenically unsaturated double bond-containing compound and thebinder.

The foregoing curable composition of the invention is cured at a highsensitivity and is satisfactory in storage stability. The curablecomposition of the invention exhibits high adhesion to the surface of ahard material such as a substrate, to which the curable composition isapplied. Accordingly, the curable composition of the invention can befavorably used in the fields of stereolithography, holography, imageforming materials inclusive of a color filter, inks, paints, adhesives,coating agents and the like.

[Color Filter]

The color filter of the invention having a colored pattern formed by thecurable composition of the invention is hereunder described along withits manufacturing method.

The color filter of the invention comprises a support having thereon acolored pattern formed using the curable composition of the invention.

The color filter of the invention is hereunder described in detailthrough its manufacturing method.

The manufacturing method of the color filter of the invention comprisesthe steps of coating the curable composition of the invention on asupport to form a curable composition layer (hereinafter properlyabbreviated as “curable composition layer forming step”); exposing thecurable composition layer through a mask (hereinafter properlyabbreviated as “exposure step”); and developing the exposed curablecomposition layer to form a colored pattern (hereinafter properlyabbreviated as “development step”).

The respective steps in the manufacturing method of the invention arehereunder described.

<Curable Composition Layer Forming Step>

In the curable composition layer forming step, the curable compositionof the invention is coated on a support to form a curable compositionlayer.

Examples of the support which can be used in this step include supportsto be used for liquid crystal display devices and the like, for example,soda-lime glass, PYREX™ glass, quartz glass and glass obtained bydepositing a transparent conductive film on such glass; photoelectricconversion device substrates to be used for imaging devices and thelike, for example, silicon substrates; and complementary metal oxidesemiconductors (CMOS). On these substrates, there may be the case whereblack stripes for isolating respective pixels are formed.

An undercoat layer may be provided on such a support for the purpose ofimproving adhesiveness to an upper layer, preventing diffusion ofsubstances or flattening the surface of the substrate as the needarises.

As a coating method of the curable composition of the invention on thesupport, various coating methods such as slit coating, an inkjet method,rotary coating, cast coating, roll coating and a screen printing methodcan be applied.

The thickness of the coating film of the curable composition ispreferably from 0.1 to 10 μm, more preferably from 0.2 to 5 μm, andfurther preferably from 0.2 to 3 μm.

Drying (pre-baking) of the photocurable composition layer coated on thesubstrate can be carried out at a temperature of from 50° C. to 140° C.for from 10 to 300 seconds by using a hot plate, an oven, etc.

<Exposure Step>

In the exposure step, the curable composition layer formed in theforegoing curable composition layer forming step is exposed through amask having a prescribed mask pattern.

As to the exposure in this step, the pattern exposure of the coatingfilm can be carried out by exposing the curable composition layerthrough a prescribed mask pattern to cure only a light exposed coatingfilm and developing it with a developing solution to form apattern-shaped film composed of pixels of respective colors (threecolors or four colors). As radiations which can be used for theexposure, in particular, ultraviolet rays such as g-line and i-line canbe preferably used. The irradiation dose is preferably from 5 to 1,500mJ/cm², more preferably 10 to 1,000 mJ/cm², and most preferably from 10to 500 mJ/cm².

In the case where the color filter of the invention is used for a liquidcrystal display device, the irradiation dose falling within theforegoing range is preferably from 5 to 200 mJ/cm², more preferably from10 to 150 mJ/cm², and most preferably from 10 to 100 mJ/cm². In the casewhere the color filter of the invention is used for a solid stateimaging device, the irradiation dose falling within the foregoing rangeis preferably from 30 to 1,500 mJ/cm², more preferably from 50 to 1,000mJ/cm², and most preferably from 80 to 500 mJ/cm².

<Development Step>

Next, by carrying out an alkaline development treatment, an unexposedarea by the exposure is eluted into an alkaline aqueous solution,whereby only a photo-cured area remains. As the developing solution, anorganic alkaline developing solution which does not damage a circuit ofthe substrate is desirable. The development temperature is usually from20° C. to 30° C., and the development time is from 20 to 90 seconds.

Examples of an alkaline agent which is used for the developing solutioninclude ammonia water and organic alkaline compounds such as ethylamine,diethylamine, dimethylethanolamine, tetramethylammonium hydroxide,tetraethylammonium hydroxide, choline, pyrrole, piperidine and1,8-diazabicyclo-[5,4,0]-7-undecene. An alkaline aqueous solutionprepared by diluting such an alkaline agent with pure water so as tohave a concentration of from 0.001 to 10% by mass, and preferably from0.01 to 1% by mass is preferably used as the developing solution. In thecase where a developing solution composed of such an alkaline aqueoussolution is used, in general, rinsing with pure water is carried outafter the development. An aqueous solution containing an inorganicalkaline compound such as sodium hydroxide, potassium hydroxide,potassium carbonate, potassium hydrogencarbonate, sodium carbonate,sodium hydrogencarbonate and calcium hydroxide can also be used.

Next, the excessive developing solution is rinsed and removed, and afterdrying, a heating treatment (post-baking) is carried out. Bysuccessively repeating the foregoing step for every color in this way, acured film can be manufactured.

There is thus obtained a color filter.

The post-baking is a heating treatment to be carried out after thedevelopment for the purpose of making the curing complete. The heatcuring treatment is usually carried out at from 100° C. to 240° C. Inthe case where the substrate is a glass substrate or a siliconsubstrate, it is preferable that the heat treatment is carried out atfrom 200° C. to 240° C. within the foregoing temperature range.

This post-baking treatment can be carried out continuously or batchwiseon the coating film after the development by using a heater such as ahot plate, a convection oven (hot air circulating oven) and ahigh-frequency heater under the foregoing condition.

After the foregoing curable composition layer forming step, exposurestep and development step, the manufacturing method of the invention mayinclude a curing step of curing the formed colored pattern upon heatingand/or exposure, if desired.

By repeating the above-described curable composition layer forming step,exposure step and development step (and further the curing step, ifdesired) for the desired hue number, a color filter composed of desiredhues is prepared.

As to applications of the curable composition of the invention, the usefor pixels of a color filter has been chiefly described. Needless tosay, the curable composition of the invention is also applicable to ablack matrix to be provided between pixels of a color filter. Except forthe addition of a black coloring agent such as carbon black and titaniumblack as a coloring agent to the curable composition of the invention,similar to the foregoing preparation method of pixels, the black matrixcan be formed by pattern exposure, alkaline development and furtherpost-baking to accelerate curing of the film.

Since the color filter of the invention is prepared using the foregoingcurable composition of the invention, the formed colored patternexhibits high adhesion to the support substrate, and the curedcomposition is excellent in development resistance. Therefore, a patternwith high resolution, which is excellent in exposure sensitivity andsatisfactory in adhesion to the substrate in an exposed area and is ableto give a desired cross-sectional shape, can be formed. Accordingly, thecolor filter of the invention can be favorably used for liquid crystaldisplay devices and solid state imaging devices such as CCD and isespecially favorable for high-resolution CCD devices or CMOS deviceswith more than 1,000,000 pixels. The color filter of the invention canbe used as a color filter to be disposed between a light-receiving partof each of pixels and a microlens for gathering light in CCD.

It is thought that since the pigment dispersion liquid of the presentinvention contains a compound having a cyclic urea structure and havingan acid group or a basic group, and this compound is adsorbed on thesurface of an organic pigment due to the cyclic urea structure thereofto effectively prevent aggregation of the pigment, excellent dispersionstability of pigment with time is achieved.

Also, it is considered that since in the pigment dispersion liquid ofthe invention, the specified compound is adsorbed on the surface of thepigment and stably dispersed, and the acid group or basic group in theforegoing compound forms an interaction with the coexisting dispersant,excellent dispersion stability is obtained even by the addition of asmall amount of a dispersion resin; and that in the curable compositionof the invention containing the foregoing pigment dispersion liquid, aratio of the polymerizable component can be relatively increased,whereby not only curing is achieved at a high sensitivity, but alsosatisfactory developability is exhibited due to the presence of theforegoing compound at the time of development.

According to the invention, even when the addition amount of the pigmentdispersant is small, a pigment dispersion liquid capable of achievingexcellent dispersion stability of pigment can be provided.

Also, by containing the pigment dispersion liquid of the invention, evenwhen the content of a pigment is large, a curable composition havingexcellent developability in an unexposed area while keeping curingsensitivity can be provided.

By using the curable composition of the invention for forming a coloredpattern, a color filter and a solid state imaging device, each of whichis provided with a high-resolution colored pattern and has sufficientcoloring density even when it is a thin layer, can be provided.

Exemplified embodiments of the present invention are as follows.

(1) A pigment dispersion liquid comprising (A) a pigment, (B) a compoundhaving a cyclic urea structure and having an acid group or a basicgroup, (C) a dispersant, and (D) a solvent.

(2) The pigment dispersion liquid according to (1), wherein the (A)pigment is (A-2) a pigment having a urea structure or an imidestructure.

(3) The pigment dispersion liquid according to (1) or (2), wherein the(A) pigment is (A-3) a pigment having a barbituric skeleton.

(4) The pigment dispersion liquid according to (1), wherein the (B)compound having a cyclic urea structure and having an acid group or abasic group is represented by the following formula (I):

wherein R¹ and R² each independently represent a hydrogen atom, asubstituted or unsubstituted alkyl group, a substituted or unsubstitutedaryl group, a substituted or unsubstituted alkenyl group or asubstituted or unsubstituted alkynyl group; and A represents a divalentlinking group that links two nitrogen atoms included in the ringstructure, wherein any one of R¹, R² and A has an acid group or a basicgroup.

(5) The pigment dispersion liquid according to (4), wherein the acidgroup or the basic group is a phenol group, a carboxyl group, a sulfonicacid group, a phosphoric acid group, a sulfinic acid group, amonosulfate ester group or an amino group.

(6) A curable composition comprising the pigment dispersion liquidaccording to any one of (1) to (5), (E) a radical polymerizablecompound, and (F) a photopolymerization initiator.

(7) A color filter comprising a colored pattern formed from the curablecomposition according to (6).

(8) A solid state imaging device comprising a colored pattern formedfrom the curable composition according to (6).

EXAMPLES

The present invention is more specifically described below withreference to the following Examples, but it should not be construed thatthe invention is limited thereto. All percentages and parts are on amass basis unless otherwise indicated.

Examples 1 to 4 and Comparative Example 1

<Preparation of Pigment Dispersion Liquid 1>

Components of the following composition (1) were mixed with stirring for3 hours using a homogenizer at a revolution number of 3,000 rpm, toprepare a mixed solution containing the (A) pigment.

[Composition (1)]

C.I. Pigment Red 254 [(A) component] 80 parts C.I. Pigment Yellow 139[(A) component] 20 parts 30% solution of cyclohexyl methacrylate/benzyl40 parts methacrylate/methacrylic acid copolymer (=45/50/5 [weightratio], weight average molecular weight: 20,000, acid value: 33) in1-methoxy-2-propyl acetate solvent [binder polymer] SOLSPERSE 24000GR(polyester based dispersant, 40 parts available from Lubrizol JapanLtd.) [(C) component] 1-Methoxy-2-propyl acetate [(D) solvent] 600 parts(B) specified compound (compound shown in Table 1) 4 parts

TABLE 1 Viscosity (B) specified compound change (mPa · s) Example 1 J-12 Example 2 J-2 4 Example 3 J-3 1 Example 4 J-4 1 Comparative None 100or more Example 1

The structures of the respective (B) specified compounds shown in theforegoing Table 1 are as follows.

Subsequently, the thus obtained mixed solution was subjected to adispersion treatment for 6 hours by a bead disperser, DISPERMAT(available from VMA Gerzmann GmbH) using 0.3-mmφ zirconia beads and thenfurther subjected to a dispersion treatment under a pressure of 2,000kg/cm³ at a flow rate of 500 g/min using a vacuum mechanism-equippedhigh-pressure disperser, NANO-3000-10 (available from Nihon B.E.E. Co.,Ltd.). This dispersion treatment was repeated 10 times to obtain redpigment dispersion compositions (Examples 1 to 5 and Comparative Example1).

<Evaluation of Pigment Dispersion Composition>

Each of the obtained pigment dispersion compositions was evaluated inthe following manner.

(1) Measurement of Viscosity and Evaluation:

With respect to each of the obtained pigment dispersion compositions, aviscosity η¹ of the pigment dispersion composition immediately afterdispersion and a viscosity η² of the pigment dispersion compositionafter an elapse of one week after dispersion (at room temperature of 25°C. to 28° C.) were measured using an E type viscometer, therebyevaluating a degree of viscosity increase. The case where a differencebetween the viscosity after an elapse of one week and the viscosityimmediately after dispersion is not more than 5 (mPa·s) is evaluated tobe good. The results obtained are also shown in Table 1.

As shown in the foregoing Table 1, it is noted that the pigmentdispersion liquids of the invention are excellent in dispersionstability of pigment with time. On the other hand, in ComparativeExample 1 which did not contain the (B) specified compound, even whenthe pigment dispersion liquid contained the (C) dispersant, it wasinferior in dispersion stability of pigment as compared with those ofthe Examples.

Examples 5 to 9 and Comparative Example 2

Examples for preparing a curable composition containing a coloring agentfor forming a color filter to be used for solid state imaging deviceusing each of the pigment dispersion liquids of Examples 1 to 4 andComparative Example 1 are hereunder described.

[2. Preparation of Color Filter]

2-1. Preparation of Undercoat Layer-Provided Silicon Substrate:

Components of the following composition were mixed and dissolved toprepare a resist solution for undercoat layer.

<Composition>

Propylene glycol monomethyl ether acetate 19.20 parts (PGMEA: solvent)Ethyl lactate 36.67 parts Binder polymer [40% PGMEA solution of benzyl30.51 parts methacrylate/methacrylic acid/2-hydroxyethyl methacrylatecopolymer (molar ratio: 60/22/18)] Dipentaerythritol hexaacrylate [(E)photopolymerizable 12.20 parts compound] Polymerization inhibitor(p-methoxyphenol) 0.0061 parts Fluorine surfactant (F-475, availablefrom Dainippon 0.83 parts Ink & Chemicals, Incorporated)Photopolymerization initiator [(F) component] (TAZ-107 0.586 parts(trihalomethyl triazine based photopolymerization initiator), availablefrom Midori Kagaku Co., Ltd.)

A 6-inch silicon wafer was subjected to a heating treatment in an ovenat 200° C. for 30 minutes. Next, the foregoing resist solution wascoated on this silicon wafer so as to have a thickness after drying of 2μm and further heated and dried in the oven at 220° C. for one hour toform an undercoat layer. There was thus obtained an undercoatlayer-provided silicon wafer substrate.

2-2. Preparation of Curable Composition (Coating Liquid):

The following components were added to each of the pigment dispersionliquids obtained in the foregoing Examples 1 to 4 and ComparativeExample 1 and mixed with stirring, to prepare curable compositionsolutions of Examples 5 to 9 and Comparative Example 2.

Pigment dispersion liquid (composition described in 100 parts Table 2)DPHA (available from Nippon Kayaku Co., Ltd.) 4.0 parts (F)Polymerization initiator (compound described in 0.5 parts Table 2) Allylmethacrylate/methacrylic acid (molar ratio: 75/25, 1.0 part weightaverage molecular weight: 57,000) [binder polymer] Surfactant (tradename: TETRANIC 150R1, available from 0.2 parts BASF AG) Solvent: PGMEA100 parts

TABLE 2 Used pigment (F) Polymeri- dispersion (B) specified zationDevelop- liquid compound initiator ability Example 5 Example 1 J-1 I-1Residue did not exist. Example 6 Example 1 J-1 I-2 Residue did notexist. Example 7 Example 2 J-2 I-1 Residue did not exist. Example 8Example 3 J-3 I-1 Residue did not exist. Example 9 Example 4 J-4 I-2Residue did not exist. Comparative Comparative None I-1 Residue Example2 Example 1 existed.

The structures of the respective polymerization initiators used in theforegoing Table 2 are as follows.

[Preparation of Color Filter by Colored Curable Composition andEvaluation Thereof]—Formation of Pattern and Evaluation of Sensitivity—

Each of the thus obtained coloring agent-containing curable compositionsof Examples 5 to 9 and Comparative Example 2 was coated on the foregoingundercoating layer-provided silicon substrate to form a curablecomposition layer (coating film). This coating film was subjected to aheating treatment (pre-baking) using a hot plate at 100° C. for 120seconds so as to have a thickness after drying of 0.9 μm.

Next, the resulting coating film was exposed at an exposure amount of100 mJ/cm² through an island pattern mask having a 1.4 μm-square patternat a wavelength of 365 nm using an i-line stepper exposure unit,FPA-3000i5+ (available from Canon Inc.) so as to obtain a 1.4 μm-squareisland pattern.

Thereafter, the silicon wafer substrate on which the irradiated coatingfilm had been formed was placed on a horizontal rotary table of aspin-shower developing machine (Model DW-30, available from ChemitronicsCo., Ltd.) and subjected to paddle development at 23° C. for 60 secondsusing CD-2000 (available from Fujifilm Electronic Materials Co., Ltd.)to form a colored pattern on the silicon wafer substrate.

The silicon wafer substrate on which a colored pattern had been formedwas fixed on the foregoing horizontal rotary table in a vacuum chuckmode, subjected to a rinse treatment by feeding pure water from anejection nozzle in a shower state from the upper side of the rotationcenter while rotating the silicon wafer substrate by a rotation unit ata revolution number of 50 rpm, and then spray dried. Thereafter, a 1.6μm-square colored pattern was formed using a length measurement SEM,S-9260A (available from Hitachi High-Technologies Corporation), and thepresence or absence of a residue in a region not irradiated with lightduring the exposure step (unexposed area) was observed, therebyevaluating the developability. The results obtained are also shown inTable 2.

As is clear from Table 2, it is noted that the curable compositions ofExamples 5 to 9 using the pigment dispersion liquid of the invention arecured under a condition at an exposure amount of 100 mJ/cm², and thusthe high sensitivity is secured, and further the developability isexcellent. On the other hand, it is noted that in the curablecomposition of Comparative Example 2 using the pigment dispersion liquidof Comparative Example 1, the residue is formed, so that sufficientdevelopability is not obtainable.

Examples 10 to 13 and Comparative Example 3

<Preparation of Pigment Dispersion Composition 2>

1-1. Kneading Dispersion Treatment of Pigment:

First of all, the following respective components were subjected to akneading dispersion treatment by twin rolls.

C.I. Pigment Green 36 [(A) pigment] 50 parts C.I. Pigment Yellow 150[(A) pigment] 50 parts Resin solution (benzyl methacrylate/methacrylicacid/ 50 parts hydroxyethyl methacrylate copolymer, molar ratio:80/10/10, Mw: 10,000, solvent: propylene glycol methyl ether acetate60%, resin solid content: 40%) SOLSPERSE 32000GR (polyester baseddispersant, available 35 parts from Lubrizol Japan Ltd.: (C) component)(D) solvent: Propylene glycol methyl ether acetate 30 parts (B)specified compound (compound shown in Table 3) 5 parts

Furthermore, the following component was added to the thus obtaineddispersion product, and the mixture was subjected to a fine dispersiontreatment the whole day and night by a sand mill. There were thusobtained pigment dispersion liquids of Examples 10 to 13 and ComparativeExample 3.

Solvent: Propylene glycol methyl ether acetate (PGMEA) 350 parts

TABLE 3 (B) specified compound or Viscosity comparative compound change(mPa · s) Example 10 J-5 3 Example 11 J-6 4 Example 12 J-7 4 Example 13J-8 2 Comparative X-1  80 Example 3

The structures of the respective (B) specified compounds and comparativecompound (X-1) described in the foregoing Table 3 are as follows.

<Evaluation of Pigment Dispersion Composition>

Each of the obtained pigment dispersion liquids of Examples 10 to 13 andComparative Example 3 was evaluated in the following manner.

(1) Measurement of Viscosity and Evaluation:

With respect to each of the obtained pigment dispersion compositions, aviscosity η¹ of the pigment dispersion composition immediately afterdispersion and a viscosity η² of the pigment dispersion compositionafter an elapse of one week after dispersion (at room temperature of 25°C. to 28° C.) were measured using an E type viscometer, therebyevaluating a degree of viscosity increase. The case where a differencebetween the viscosity after an elapse of one week and the viscosityimmediately after dispersion is not more than 5 (mPa·s) is evaluated tobe good. The results obtained are also shown in Table 3.

As shown in the foregoing Table 3, it is noted that the pigmentdispersion liquids of the invention are excellent in dispersionstability of pigment with time. On the other hand, in ComparativeExample 3 which contained the comparative compound (X-1) in place of the(B) specified compound, though the pigment dispersion liquid was moreimproved in stability than that of Comparative Example 1, it wasinferior in dispersion stability of pigment as compared with those ofthe Examples.

Examples 14 to 17 and Comparative Example 4

[Preparation of Color Filter]

Examples for preparing a curable composition containing a coloring agent(dye) for forming a color filter to be used for a solid state imagingdevice using each of the pigment dispersion liquids of Examples 10 to 13and Comparative Example 3 are hereunder described.

2-1. Preparation of Undercoat Layer-Provided Silicon Substrate:

Components of the following composition were mixed and dissolved toprepare a resist solution for undercoat layer.

<Composition>

Propylene glycol monomethyl ether acetate 19.20 parts (PGMEA: solvent)Ethyl lactate 36.67 parts Binder polymer [40% PGMEA solution of benzyl30.51 parts methacrylate/methacrylic acid (molar ratio: 75/25)]Dipentaerythritol hexaacrylate [(E) photo- 12.20 parts polymerizablecompound] Polymerization inhibitor (p-methoxyphenol) 0.0065 partsFluorine surfactant (F-475, available from Dainippon 0.80 parts Ink &Chemicals, Incorporated) (F) Photopolymerization initiator (compounddescribed 0.50 parts in Table 4)

A 6-inch silicon wafer was subjected to a heating treatment in an ovenat 200° C. for 30 minutes. Next, the foregoing resist solution wascoated on this silicon wafer so as to have a thickness after drying of 2μm and further heated and dried in the oven at 220° C. for one hour toform an undercoat layer. There was thus obtained an undercoatlayer-provided silicon wafer substrate.

2-2. Preparation of Curable Composition (Coating Liquid):

The following components were added to each of the foregoing pigmentshaving been subjected to a dispersion treatment and mixed with stirring,to prepare a curable composition solution.

Foregoing pigment dispersion liquid 100 parts Pentaerythritoltetraacrylate 3.8 parts (F) photopolymerization initiator (compounddescribed 0.5 parts in Table 4) Benzyl methacrylate/methacrylic acid(molar ratio: 0.7 parts 70/30, weight average molecular weight: 70,000)Surfactant (trade name: TETRANIC 150R1, available from 0.2 parts BASFAG) Solvent: PGMEA 100 parts

TABLE 4 Used (B) specified pigment compound or (F) Polymeri- dispersioncomparative zation Develop- liquid compound initiator ability Example 14Example 10 J-5 I-1 Residue did not exist. Example 15 Example 11 J-6 I-2Residue did not exist. Example 16 Example 12 J-7 I-1 Residue did notexist. Example 17 Example 13 J-8 I-2 Residue did not exist. ComparativeComparative X-1  I-1 Residue Example 4 Example 3 existed.

The polymerization initiators used in the foregoing Table 4 are the samecompounds as those used in the foregoing Table 2.

[Preparation of Color Filter by Colored Curable Composition andEvaluation Thereof]

—Formation of Pattern and Evaluation of Sensitivity—

Each of the thus obtained coloring agent-containing curable compositionsof Examples 14 to 17 and Comparative Example 4 was coated on theforegoing undercoating layer-provided silicon substrate to form acurable composition layer (coating film). This coating film wassubjected to a heating treatment (pre-baking) using a hot plate at 100°C. for 120 seconds so as to have a thickness after drying of 0.9 μm.

Next, the resulting coating film was exposed at an exposure amount of100 mJ/cm² through an island pattern mask having a 1.4 μm-square patternat a wavelength of 365 nm using an i-line stepper exposure unit,FPA-3000i5+ (available from Canon Inc.) so as to obtain a 1.4 μm-squareisland pattern.

Thereafter, the silicon wafer substrate on which the irradiated coatingfilm had been formed was placed on a horizontal rotary table of aspin-shower developing machine (Model DW-30, available from ChemitronicsCo., Ltd.) and subjected to paddle development at 23° C. for 60 secondsusing CD-2000 (available from Fujifilm Electronic Materials Co., Ltd.)to form a colored pattern on the silicon wafer substrate.

The silicon wafer substrate on which a colored pattern had been formedwas fixed on the foregoing horizontal rotary table in a vacuum chuckmode, subjected to a rinse treatment by feeding pure water from anejection nozzle in a shower state from the upper side of the rotationcenter while rotating the silicon wafer substrate by a rotation unit ata revolution number of 50 rpm, and then spray dried. Thereafter, a 1.6μm-square colored pattern was formed using a length measurement SEM,S-9260A (available from Hitachi High-Technologies Corporation), and thepresence or absence of a residue in a region not irradiated with lightduring the exposure step (unexposed area) was observed, therebyevaluating the developability. The results obtained are also shown inTable 4.

As is clear from Table 4, it is noted that the curable compositions ofExamples 14 to 17 using the pigment dispersion liquid of the inventionare excellent in developability. On the other hand, it is noted that inthe curable composition of Comparative Example 4 using the pigmentdispersion liquid of Comparative Example 3, the residue is formed, sothat sufficient developability is not obtainable.

Examples 18 to 21 and Comparative Example 5

<Preparation of Pigment Dispersion Composition 3>

Components of the following composition (1) were mixed with stirring for3 hours using a homogenizer at a revolution number of 3,000 rpm, toprepare a mixed solution containing a pigment.

[Composition (1)]

C.I. Pigment Red 254 [(A) component] 80 parts C.I. Pigment Yellow 139[(A) component] 20 parts Benzyl methacrylate/methacrylic acid/terminal20 parts methacryloylated polymethyl methacrylate copolymer (AA-6,available from Toagosei Co., Ltd., weight ratio: 15/10/75, weightaverage molecular weight: 20,000, acid value: 52) (polymer 1) SOLSPERSE24000GR (polyester based dispersant, 30 parts available from LubrizolJapan Ltd.) [(C) component] (B) specified compound (compound shown inTable 5) 3 parts 1-Methoxy-2-propyl acetate 820 parts

Subsequently, the thus obtained mixed solution was subjected to adispersion treatment for 6 hours by a bead disperser, DISPERMAT(available from VMA Gerzmann GmbH) using 0.3-mmφ zirconia beads and thenfurther subjected to a dispersion treatment under a pressure of 2,000kg/cm³ at a flow rate of 500 g/min using a vacuum mechanism-equippedhigh-pressure disperser, NANO-3000-10 (available from Nihon B.E.E. Co.,Ltd.). This dispersion treatment was repeated 10 times to obtain a redpigment dispersion composition.

TABLE 5 Viscosity (B) specified compound change (mPa · s) Example 18J-9  3 Example 19 J-10 4 Example 20 J-11 4 Example 21 J-12 2 ComparativeNone 80 Example 5

The details of the respective (B) specified compounds used in Examples18 to 21 are shown below.

<Evaluation of Pigment Dispersion Composition>

Each of the obtained pigment dispersion liquids was evaluated in thefollowing manner.

(1) Measurement of Viscosity and Evaluation:

With respect to each of the obtained pigment dispersion compositions, aviscosity η¹ of the pigment dispersion composition immediately afterdispersion and a viscosity η² of the pigment dispersion compositionafter an elapse of one week after dispersion (at room temperature) weremeasured using an E type viscometer, thereby evaluating a degree ofviscosity increase. The evaluation results obtained are also shown inthe foregoing Table 5. Here, small viscosity change means that thedispersion stability is good.

It is noted from Table 5 that the pigment dispersion liquids of theinvention are excellent in dispersibility and dispersion stability ofpigment.

Examples 22 to 25 and Comparative Example 6

<2. Preparation of Color Filter>

2-1. Preparation of Curable Composition (Coating Liquid):

The following components were added to each of the foregoing pigmentshaving been subjected to a dispersion treatment and mixed with stirring,to prepare a curable composition solution.

Foregoing pigment dispersion liquid 100 parts DPHA (available fromNippon Kayaku Co., Ltd.) 3.8 parts (F) photopolymerization initiator(compound 1.5 parts or 2.5 parts described in Table 6) Benzylmethacrylate/methacrylic acid (molar ratio: 0.7 parts 70/30, weightaverage molecular weight: 70,000) Surfactant (trade name: TETRANIC150R1, 0.2 parts available from BASF AG) Solvent: PGMEA 100 parts

TABLE 6 Used (F) Polymeri- pigment zation dispersion (B) specifiedinitiator Develop- liquid compound (content: parts) ability Example 22Example 18 J-9  I-1 Residue did (1.5) not exist. Example 23 Example 19J-10 I-3 Residue did (1.5) not exist. Example 24 Example 20 J-11I-4/D-1/S-1 Residue did Weight ratio not exist. (1/1/1) (2.5) Example 25Example 21 J-12 I-4/D-2/S-2 Residue did Weight ratio not exist. (1/1/1)(2.5) Comparative Comparative None I-3 Residue Example 6 Example 5 (1.5)existed.

The photopolymerization initiator (I-3) used in the foregoing Table 6 is4-benzoxolan-2,6-di(trichloromethyl)-s-triazine. The structures of otherphotopolymerization initiators in Table 6 are as follows.

2-2. Formation of Curable Composition Layer:

The foregoing pigment-containing curable composition was slit coated asa resist solution on a glass substrate of 550 mm×650 mm under thefollowing condition, and allowed to stand for 10 minutes as it was, andsubjected to vacuum drying and pre-baking (at 100° C. for 80 seconds) toform a curable composition coating film (curable composition layer).

(Slit Coating Condition)

Gap of opening of tip of coating head: 50 μm Coating speed: 100 mm/secClearance between substrate and coating head: 150 μm Coating thickness(thickness after drying): 2 μm Coating temperature: 23° C.2-3. Exposure and Development:

Thereafter, the photocurable coating film was pattern exposed through aphotomask for testing having a line width of 20 μm using a 2.5 kWextra-high mercury vapor lamp, and after the exposure, the entiresurface of the coating film was covered by a 1% aqueous solution of analkaline developing solution, CDK-1 (available from Fujifilm ElectronicMaterials Co., Ltd.) and allowed to stand for 40 seconds.

2-4. Heating Treatment:

After standing, pure water was sprayed in a shower state to wash awaythe developing solution, and the coating film having been subjected tosuch photocuring treatment and development treatment was heated in anoven at 220° C. for one hour (post-baking). There was thus obtained acolored resin film (color filter) on the glass substrate.

[3. Evaluation of Performance of Color Filter]

The storage stability of the thus prepared colored curable compositioncoating liquid and a residue in an unexposed area of the curablecomposition coating film (colored layer) formed on the glass substrateusing the colored curable composition after exposure at an exposureamount of 100 mJ/cm², developing and post-baking were confirmed.

As is clear from Table 6, it is noted that the curable compositions ofExamples 22 to 25 using the pigment dispersion liquid of the inventionare excellent in developability. On the other hand, it is noted that inthe curable composition of Comparative Example 6 using the pigmentdispersion liquid of Comparative Example 5, the residue is formed, sothat sufficient developability is not obtainable.

1. A color filter comprising a colored pattern formed from a curablecomposition comprising (A) a pigment, (B) a compound having a cyclicurea structure and having an acid group or a basic group, (C) adispersant, (D) a solvent, (E) a radical polymerizable compound, and (F)a photopolymerization initiator, wherein the (B) compound having acyclic urea structure and having an acid group or a basic group isrepresented by the following formula (l):

wherein R¹ and R² each represent a hydrogen atom: and A represents adivalent linking group that links two nitrogen atoms included in thering structure wherein A has an acid group or a basic group.
 2. Thecolor filter according to claim 1, wherein the (A) pigment is (A-2) apigment having a urea structure or an imide structure.
 3. The colorfilter according to claim 1, wherein the (A) pigment is (A-3) a pigmenthaving a barbituric skeleton.
 4. The color filter according to claim 1,wherein the acid group or the basic group is a phenol group, a carboxylgroup, a sulfonic acid group, a phosphoric acid group, a sulfinic acidgroup, a monosulfate ester group or an amino group.
 5. The color filteraccording to claim 1, wherein the (A) pigment is selected from the groupconsisting of Pigment Green 36, Pigment Yellow 139, Pigment Yellow 150and Pigment Yellow
 185. 6. The color filter according to claim 1,wherein (B) is a compound having a cyclic urea structure and having anacid group.
 7. The color filter according to claim 6, wherein the acidgroup is selected from the group consisting of a carboxyl group, asulfonic acid group and salts thereof.
 8. The color filter according toclaim 1, wherein the (B) compound having a cyclic urea structure andhaving an acid group or a basic group is represented by the followingformula (III):

wherein R¹ and R² each represent a hydrogen atom; and R⁴ and R⁵ eachrepresent a hydrogen atom, or an alkyl group, an aryl group, an alkenylgroup or an alkynyl group, wherein each of R⁴ and R⁵ may further have asubstituent selected from the group consisting of an alkyl group, anaryl group, an alkenyl group, an alkynyl group, a cyclic alkyl group, acyclic alkenyl group, a cyclic alkynyl group, a hydroxyl group, a thiolgroup, an ether group, a thioether group, a sulfo group, a sulfonamidegroup, a carbonyl group, an alkoxycarbonyl group, an aryloxycarbonylgroup, a thiocarbonyl group, a urea group, a urethane group, an amidegroup, and a heterocyclic group, wherein R⁴ or R⁵ contains an acid groupor a basic group.
 9. A solid state imaging device comprising a coloredpattern formed from a curable composition comprising (A) a pigment, (B)a compound having a cyclic urea structure and having an acid group or abasic group, (C) a dispersant, (D) a solvent, (E) a radicalpolymerizable compound, and (F) a photopolymerization initiator, whereinthe (B) compound having a cyclic urea structure and having an acid groupor a basic group is represented by the following formula (I):

wherein R¹ and R² each represent a hydrogen atom: and A represents adivalent linking group that links two nitrogen atoms included in thering structure wherein A has an acid group or a basic group.
 10. Thesolid state imaging device according to claim 9, wherein the (A) pigmentis (A-2) a pigment having a urea structure or an imide structure. 11.The solid state imaging device according to claim 9, wherein the (A)pigment is (A-3) a pigment having a barbituric skeleton.
 12. The solidstate imaging device according to claim 9, wherein the acid group or thebasic group is a phenol group, a carboxyl group, a sulfonic acid group,a phosphoric acid group, a sulfinic acid group, a monosulfate estergroup or an amino group.
 13. The solid state imaging device according toclaim 9, wherein the (A) pigment is selected from the group consistingof Pigment Green 36, Pigment Yellow 139, Pigment Yellow 150 and PigmentYellow
 185. 14. The solid state imaging device according to claim 9,wherein (B) is a compound having a cyclic urea structure and having anacid group.
 15. The solid state imaging device according to claim 14,wherein the acid group is selected from the group consisting of acarboxyl group, a sulfonic acid group and salts thereof.
 16. The solidstate imaging device according to claim 9, wherein the (B) compoundhaving a cyclic urea structure and having an acid group or a basic groupis represented by the following formula (III):

wherein R¹ and R² each represent a hydrogen atom; and R⁴ and R⁵ eachrepresent a hydrogen atom, or an alkyl group, an aryl group, an alkenylgroup or an alkynyl group, wherein each of R⁴ and R⁵ may further have asubstituent selected from the group consisting of an alkyl group, anaryl group, an alkenyl group, an alkynyl group, a cyclic alkyl group, acyclic alkenyl group, a cyclic alkynyl group, a hydroxyl group, a thiolgroup, an ether group, a thioether group, a sulfo group, a sulfonamidegroup, a carbonyl group, an alkoxycarbonyl group, an aryloxycarbonylgroup, a thiocarbonyl group, a urea group, a urethane group, an amidegroup, and a heterocyclic group, wherein R⁴ or R⁵ contains an acid groupor a basic group.